Diacylaminophenol couplers



Nov. 27, 195.6

OPT/CAL DENSITY OPT/CAL DEA SIT) I. F. SALMINEN ETAL DIACYLAMINOPHENOL.COUPLERS Filed Nov. 3,

Fig

l i 500 600 WAVELENGTH //V M/LL/M/CROA/S Fig. 2

500 600 WAVELENGTH l/V M/LL/M/CROA/S DYE FROM ACYLAM/NOPHE/VOL (PR/0RART) DYE 'FROM 2,5D/ACYLAMl/VOPHE/VOL /L MARI F SALMI/VE/V CHARLES R.BAR/P INVENTORS $2 k BY 2 fl AUT /1" Ers United States PatentDIACYLAMINOPHENOL COUPLERS Ilmarl F. Salminen and Charles R. Barr,Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey Application November 3, 1954, Serial No.466,570 Claims. (CI. 96-55) This invention relates to color photographyand particularly to certain diacylaminophenol coupler compounds.

The formation of colored photographic images by con pling thedevelopment product of primary aromatic amino developing agents withcolor forming or coupling compound-s is well known. In these processesthe subtractive process of color formation is ordinarily used and theimage dyes are intended to be of complementary primary colors cyan,magneta and yellow. The couplers used to produce the cyan dyes areusually phenols or naphthols and produce indophenol dyes upon couplingwith the development product of the developing agent.

Aminonaphthols have been used as cyan-forming couplers but the heatstability of the dye images formed from them in usually low.Acylaminophenols of the type described in Salminen and Weissberger U. S.Patent 2,423,730, granted July 8, 1947, have also been used, but thedyes produced from these couplers have a rather high absorption in theblue spectral region and also have a somewhat low degree of heatstability. It is, of course, desirable for the absorption of the cyandyes to be low in the blue region and for the heat stability to be ashigh as possible.

It is, therefore, an object of the present invention to provide novelphotographic coupler compounds for producing cyan dye images. A furtherobject is to provide coupler compounds which produce cyan dyes havinglow blue light absorption. A still further object is to provide couplercompounds which produce dyes having a high degree of heat stability.Other objects will appear from the following description of ourinvention.

These objects are accomplished according to our in- 2,772,162 PatentedNov. 27, 1956 Specific compounds which we may use are those in which Xand Y have the structure shown below:

CsHu-t HO 0 CH5:

2-acetamido-5- [u- 2,4-di-tert-am ylphenoxy acetamido] phenol C sHutCaHCONH vention by the use of certain diacylaminophenol described below,as coupler compounds.

The accompanying drawing is a reproduction of spectral absorption curvesof dye images produced from a typical coupler of the present invention(Fig. 2) and comparison curves of a dye image made from a prior artcoupler (Fig. 1), before and after subjecting them to fading tests.

Couplers of the following structure are useful according to ourinvention:

NHX

YEN

in which X=fatty acid acyl aromatic carboxylic acyl aryloxy-substitutedfatty acid acyl Y=fatty acid acyl Y aromatic carboxylic acylaryloxy-substituted fatty acid acyl phenylcarbamyl fatty acid acylfuroyl CBHlk't NH 0 0 CH6 O(CHa)aGONH Cs n 2-benzamid0-5- ['1-(2,4-di-tert-amylphenoxy) butyrainido] phenol 5-benzamido-2- [n-(2,4-di-tert-arnylphenoxy butyramido] phenol CIH5C ONE NBC 0 OH:

11:0 0 OHN 2,5-di-aeetamido-phenol s. OH

' NHOO(CH2)4CH mmOm-(omho CHN Os u 2-caproylamido-5- ['y-(2,4-di-tert-amy1phen0xy) butyramido1- phenol2,5-di-palmitoylamido-phenol The couplers of our invention are producedby treating Z-amino-S-nitrophenol (BeiL, 13, 390) with the appropriateacyl chloride, reducing the nitro group to an amine and then treatingwith the same or a difierent acyl chloride. The preparation of thecompounds of our invention is illustrated by the follo ring examples:

C ozlpler 1 .2-acezamid0-5- a- (2,4-di-tert-amylphenoxy acetamido]-phenl To a solution of 1 part of Z-acetamido-S-aminophenol and 1.5parts of anhydrous sodium acetate in 20 volumes of glacial acetic acidwas added a solution of 2 parts of 2,4-di-tert-amylphenoxyacetylchloride in 10 volumes of glacial acetic acid. The temperature rose from25-32" and a White solid separated. The mixture was stirred for one-halfhour and poured into 100 volumes of Water. The gummy solid was collectedand recrystallized from 25 volumes of absolute ethyl alcohol and dried.

Z-acetamido-5-nitr0phenol To a mixture of 6 parts of2-amino-5-nitrophenol (Beil, 13, 390), 8 parts of anhydrous sodiumacetate, and 60 volumes of glacial acetic acid was added, with stirring,a solution of 3 parts of acetyl chloride in 20 volumes of glacial aceticacid. The reaction mixture was stirred for one hour, and the productwhich separated was filtered, washed with water, and dried.

Z-acetamido-S-aminophenol In a :700-cc. low-pressure reduction bottlewas placed a solution of one part of 2-acetamido-5-nitrophenol in 25volumes of dioxane. To this solution was added one part of Raney nickelcatalyst, and the bottle was placed on the Parr hydrogenation apparatus.The hydrogen pressure was brought up to 50 lb. and shaking commenced.The reduction was complete after approximately one hour. The mixture wasfiltered, and the filtrate was concentrated in vacuo on steam. The solidresidue was dried to constant weight in air at room temperature.

2,4-di-tert.-amylphenoxy acetic acid In a 3-1 three-necked flaskequipped with a stirrer, thermometer, and reflux condenser was placed 40cc. of water and 660 cc. of denatured alcohol, and 80' g. (2.0 moles) ofsodium hydroxide. The solution was stirred, 234 g. (1.0 mole) ofredistilled 2,4-di-tert.-amylphenol was added and the solution refluxedfor five minutes. It was then cooled to 60 and 94.5 g. (1.0 mole) ofchloroacetic acid added. The mixture was refiuxed with stirring forthree hours, cooled to room temperature, diluted with 1 liter of icewater and acidified with 200 cc. of concentrated hydrochloric acid. Thediarnylphenoxy acetic acid, separated as an orange-brown oil, wasextracted with 200 cc. of ether and the wet ether layer concentratedunder reduced pressure on the steam-bath. The heavy oil Was vacuumdistilled, collecting at 172-176" at l mmJHg. Yield: 127 g. (43%). Theviscous oil soon solidified to a wax-like solid. The diamylphenoxyacetic acid can be purified by recrystallization from hexane, M. P.116-117"; snow-white powder.

a- (2,4-di-zert.-amy lphcnoxy acetyl chloride Eighty grams (0.27 mole of2,4-di-tert.-amylphenoxy) acetic acid was melted on the steam-bath andcooled to 50. To the semi-solid was added 88 g. (0.74 mole) of thionylchloride (redistilled over quinoline) and the mixture stirred until allof the solid dissolved. The clear liquid was placed in a 500 cc. flaskequipped with stirrer and thermometer and heated with stirring at 40-45for 4 hours. Excess thionyl chloride was removed by warming underreduced pressure at a water pump. The product was collected at 143-l46/2mm. Yield 65 g. (76.5%).

To a solution of 2 parts of 5-arnino-2--(lA-di-tertamylphenoxy)butyramidolphenol and 1.3 parts of quinoline in36 volumes of dioxane was added 0.71 part of benzoyl chloride in 11volumes of dioxane. The temperature rose fromv 26-31". The clearreaction mixture was stirred for one-half hour and poured into 400volumes of dilute hydrochloric acid. The solid product was collected andrecrystallized from 114 volumes of acetonitrile and dried.

'y (2,4-rli-tert-amylph enoxy blltyric acid in a suitable vesselprovided with stirrer, thermometer, and coil condenser were placed 500volumes of absolute methyl alcohol and 46 parts of sodium. To the sodiummethoxide thus. made was added 468 parts of 2,4-di-tertamylphenol andstirred 15 minutes. Butyrolactone (198 parts) was added and the mixturerefluxed 15 minutes. The condenser was inverted and the excess methylalcohol distilled up to 115. Concentrated hydrochloric acid (500volumes) in 1400 volumes of distilled water was added continuously withstirring, and. the acidic mixture poured into a glass tray to cool. Thesolid was washed and filtered, 650 parts being obtained. The product wascrystallized from 1500 volumes of ligroin, 300 grams of product meltingat 98-100 being obtained.

'y (2,4-di-tert-amylphenoxy) butyryl chloride In a suitable vessel,provided with a condenser, was placed 32 parts of'y-[2,4-di-tert-arnylphenoxy)butyric acid to which was added 22 volumesof thionyl chloride. The mixture was heated for 3 hours at 40; at theend of this time the excess thionyl chloride was removed under vacuum,the temperature being allowed to reach 55. The crude acid chloride waspurified by distillation, B. P. -166/l mm.

2- ['y- (2,4-di-tert-amylphenoxy) butyramido l -5-rritrophenol To asolution of 3 parts of 2-amino-5-nitrophenol (Beil., 13, 390), 5 partsof quinoline, and 50 volumes of dioxane was added a solution of 7 partsof 'y(2,4dltert-amylphenoxy)butyryl chloride in 10 volumes of dioxane.The reaction mixture was stirred at room temperature for one-half hour,and poured into 300 volumes of dilute hydrochloric acid. The oil whichseparated solidified on scratching, was filtered, washed with water, anddried.

5 -amin0-2 ['y- (2,4-d i-tert-amyl ph enoxy) bzztyram-ido] phenol In a500-cc. low-pressure reduction bottle was placed 10 parts of 2-[--(2,4-di-tert-amylphenoxy)butyramido-S- nitrophenol in 250 volumes ofabsolute ethyl alcohol. To this solution was added one part of Raneynickel catalyst, and the bottle was placed on the Parr hydrogenationapparatus. The hydrogen pressure was brought up to 50 lb. The reductionwas completed after approximately one hour. The mixture was filtered,and the filtrate was concentrated in vacuo on steam. The residual solidwas slurried in petroleum ether, and dried.

Coupler 3 .-2 benzam id0-5- ['y- (2 ,4-di-tert-amylphenoxy) butyramido]-phen0l To a solution of 4.5 parts of 5-amino-2-benzamidophenol in 100volumes of dioxane were added simultaneously at 10 C. a solution of 5parts of quinoline in 10 volumes of dioxane and a solution of 6.8 partsof -(2,4-di-tert-amylphenoxy)butyryl chloride in 10 vol umes of dioxane.The temperature rose to 20 C. The

I clear reaction mixture was left to stand for 2 days and poured into500 volumes of dilute hydrochloric acid. The solid product was collectedand recrystallized from 150 volumes of acetonitrile and dried.

2-benzamido-S-nitrophenol To a solution of 3 parts of2-amino-5-nitrophenol (Beil., 13, 390) and 5 parts of quinoline in 60volumes of dioxane was added a solution of 3 parts of benzoyl chloridein 10 volumes of dioxane. The mixture was stirred for approximately onehour, after which time it was poured into 250 volumes of dilutehydrochloric acid. The solid which separated was filtered, washed withwater, and dried.

5 -amid-2-benzamidophenol In a SOD-cc. low-pressure reduction bottle wasplaced 10 parts of 2-benzamido-S-nitrophenol in 200 volumes of dioxane.To this solution was added one part of Raney nickel catalyst, and thebottle was placed on the Parr hydrogenation apparatus. The hydrogenpressure was brought up to 50 lb. The reduction was completed afterapproximately one hour. The mixture was filtered, and the filtrate waskept under CO2 until the amine was used in preparing the final coupler.

Coupler 4 .5 -benzamido-2- [a- (2,4-di-tert-amylph enoxy) butyramido]-phen0l To a solution of 7 parts of5-amino-2-[or-(2,4-di-tertamylphenoxy)butyramidolphenol and 4 parts ofquinoline in 50 volumes of dioxane was added a solution of 2.3 parts ofbenzoyl chloride in volumes of dioxane. The temperature rose from 3038.The clear reaction mixture was stirred for 3 hours and poured into 300volumes of dilute hydrochloric acid. The gummy product was collected andrecrystallized from 125 volum of acetonitrile and dried.

2- [u- (2,4-di-tert-amylphenoxy) butyramido] 5-nitr0phenol To a solutionof 3 parts of Z-amino-S-nitrophenol (BeiL, 13, 390) and 5 parts ofquinoline in 40 volumes of dioxane was added a solution of 6 parts ofu-(2,4-ditert-amylphenoxy) butyryl chloride (see Fierke and ChechakSerial No. 476,561 filed December 20, 1954) in 20 volumes of dioxane Themixture was stirred for approximately one hour and left standing at roomtemperature overnight, after which time it was poured into 250 volumesof dilute hydrochloric acid. The solid which separated was filtered,washed with water, and dried.

5 -amin0-2- [oz- (2,4-di-tert-amylphenoxy butyramido] phenol In a500-cc. low-pressure reduction bottle was placed 10 parts of2-[u-(2,4-di-tert-amylphenoxy)butyramidol- 5-nitrophenol in 100 volumesof dioxane. To this solution was added 1 part of Raney nickel catalyst,and the bottle was placed on'the Parr hydrogenation apparatus. Thehydrogen pressure was brought up to 50 lb., and the reduction wascompleted after approximately one hour. The mixture was filtered, andthe filtrate was kept under CO2 until the amine was used in preparingthe final coupler.

Coupler 10.2 .5-di- [cz- (2,4-di-tert-amylphenoxy) acetamido] -phen0l Toa solution of 8 parts of 5-amino-2-[oz-(2,4-di-tertamylphenoxy)acetamidolphenol and 5 parts of quinoline in 50 volumes of dioxane wasadded 6 parts of a-(2,4-ditert-amylphenoxy) acetyl chloride in 20 volumeof dioxane. The mixture was left standing at room temperature overnight,during which time some solid separated. The mixture was then poured into125 volumes of dilute hydrochloric acid, and the solid which separatedWas filtered, washed with water, and dried.

2- [a- (2,4-di-tert-amylphenoxy) acetamido] -5n itrophenol 5 -amin0-2-[a (2,4-di-tert-amylphenoxy acetamz'do] phenol In a SOO-cc. low-pressurereduction bottle was placed 8 parts of2-[u-(2,4-di-tert-amylphenoxy)acetamidol-S- nitrophenol in 200 volumesof ethyl acetate. To this solution was added 1 part of Raney nickelcatalyst, and the bottle was placed on the Parr hydrogenation apparatus.

The hydrogen pressure was brought up to 50 1b., and the reduction wascompleted after approximately one hour.

The mixture was filtered, and the filtrate was concentrated in vacuo andair-dried.

Coupler 19.2,5-di- [a-(2,4-di-tert-amylphenoxy) acetamido]-4-(Z-carbethoxyphenylazo) phenol To the solution of 3 parts of2,5-di-[a-(2,4-di-tertamylphenoxy)acetamidolphenol (coupler No. 10) in25 volumes of pyridine at 0 C. was added a solution of 1 part ofo-carbethoxybenzenediazonium chloride in 10 volumes of pyridine. Thismixture was left standing at room temperature for one hour, after whichtime it was diluted with volumes of water. The product which separatedwas filtered and dried.

Coupler 20.-5-(S-chlorosulfonylbenzamido)- Z-stearamidophenol To thesolution of 3.9 parts of S-amino-Z-stearamidophenol and 2.6 parts ofquinoline in 60 volumes of dioxane was added a solution of 2.5 parts of3-chlorosulfonylbenzoyl chloride in 15 volumes of dioxane with stirringat 25 C. The temperature rose rapidly to 33 C. and a complete solutionresulted. In about five minutes a thick light tan slurry formed. Themixture was left standing at room temperature overnight, after whichtime the solid was filtered 01f andslurried in 100 volumes of water anddried. This solid was recrystallized from ethyl acetate.

The remaining compounds were prepared similarly, using the followingacyl chlorides: Acetyl chloride for coupler 5, caproyl chloride forcouplers 6, ll, 16 and 17, lauroyl chloride for couplers 7 and 8,palmitoyl chloride for coupler 9, furoyl chloride for coupler 8,'y-2,4-di-tertamylphenoxy butyryl chloride for couplers 6, 11, 12, 13and 15, a-2,4-di-tert-amylphenoxy butyryl chloride for couplers 14, 16and 17, p-tert-amylbenzoyl chloride for couplers l3 and 15,chloro-2,4-di-tert-amylphenoxy-acetyl chloride for coupler 18, and5-3,5-dicarbomethoxy phenyl carbamyl valeryl chloride for coupler 12.This intermediate was prepared as described in U. S. Patent 2,688,544.The couplers or our invention are preferably incorporated in thephotographic emulsion layers by dissolving them in a Water-insoluble,water-permeable solvent and dlspersing the resulting solution in theemulsion layer. Water-insoluble, water-permeable solvents for thecouplers include materials such as cellulose esters, natural andsynthetic resins and high boiling crystalloidal mate-' EXAMPLE 1 Onegram of coupler No. 11 was dissolved in a mixture of 4 cc. of2,4-di-tert-amylphenol and 50 cc. of ethyl ace-2-amino-5-diethylaminotoluene HCl grams 2 Sodium sulfite (desiccated) do2 Sodium carbonate, monohydrate do 20 Potassium bromide do 2 Water toliter 1 After development, the emulsion was fixed .in the usualacid-alum fixing bath, washed, and the silver removed by successivetreatments in ferricyanide-bromide solution and hypo.

EXAMPLE 2 Certain of the couplers of our invention may be incorporatedin the developing solution, where no coupler is present in the emulsionlayer as in certain processes. A developing solution suitable fordeveloping the fine image is as follows:

2-amino-S-diethylaminotoluene grams 2 Sodium sulfite, anhydrous do 2Sodium carbonate, monohydrate do 20 Potassium bromide do 1 Water toliter 1 Coupler NO. 5 grams 2 Sodium hydroxide, solution cc 10 For use,B is added to A The value of our couplers in producing dyes which haveless blue absorption and which are more stable to heat treatment isillustrated in the drawing. As shown therein, Fig. 1 illustrates thecurves obtained upon development of an emulsion layer containing thecoupler Z-[a- (4 tert. amylphenoxy) n-butyryl amino] -4-chloro-5- methylphenol (Compound of U. S. Patent 2,423,730), incorporated in theemulsion and developed as described in Example 1. A illustrates thecurve obtained immediately after development and B illustrates the curveobtained after treatment of the emulsion at 140 F. for one week. Theblue light absorption between 400 and 500 millimicrons is appreciable inboth cases but the red light absorption in the region about 460 to 480millimicrons is considerably lower after heat storage, showing that thedye has faded to an appreciable extent.

Fig. 2 illustrates the curves obtained upon treatment in an identicalmanner of an emulsion containing coupler No. 16 of the presentinvention. In this case, the blue light absorption between 200 and 400millimicrons is lower than in the previous case and the absorption inthe red spectral region has not changed appreciably upon heat treatmentfrom curve A illustrating the absorption of the dye immediately afterdevelopment to curve B illustrating the dye after heat storage as in thepreceding case. This illustrates the improved stability obtained withdyes made from our couplers.

Our couplers may be incorporated in gelatino-silver halide emulsionlayers or in silver halide emulsions or other carriers such as organicacid esters of cellulose or synthetic resins. The support may be atransparent medium such as glass or cellulose ester or a non-transparentreflecting medium such as paper or an opaque cellulose ester. Theemulsion may be coated as a single layer on the support or superposedlayers may be coated on one or both sides of the support. The superposedlayers may be differentially sensitized to form a natural color elementin the known manner. Our couplers produce cyan dyes and will usually beincorporated in the red-sensitive emulsion layer of a multi-layercoating or they may be incorporated in layers otherwise sensitized whenfalse colors are to be produced.

The examples and compounds set forth in the present specification areillustrative only and it is to be understood that our invention is to betaken as limited only by the scope of the appended claims.

We claim:

1. The method of producing a cyan photographic image in silver halideemulsion layer, which comprises exposing the layer and developing itwith a primary aromatic amino developing agent in the presence of a2.,5-diacylaminophenol coupler compound, in which the acyl is derivedfrom carboxylic acid.

2. The method of producing a cyan photographic image in silver halideemulsion layer, which comprises exposing the layer and developing itwith a primary aromatic amino developing agent in the presence of acoupler compound having the formula:

in which X is selected from the class consisting of fatty acid acylradicals, aromatic carboxylic acyl radicals and aryloxy-substitutedfatty acid acyl radicals, and Y is selected from the class consisting offatty acid acyl radicals, aromatic carboxylic acyl radicals,aryloxy-substituted fatty acid acyl radicals, phenylcarbamyl fatty acidacyl radicals and furoyl radicals.

3. The method of producing a cyan photographic image in silver halideemulsion layer, which comprises exposing the layer and developing itwith a primary aromatic amino developing agent in the presence in saidemulsion layer prior to development, of a coupler compound having theformula:

NHOOR R'OCHN in which R represents an alkyl radical of from 4 to 15carbon atoms and R represents an aryloxyalkyl radical in which the alkylradical contains from 1 to 3 carbon atoms.

4. The method of claim 3 in which the aryloxy radical is a 2-4-di-tert.amyl phenoxy radical.

5. The method of producing a cyan photographic image in silver halideemulsion layer, which comprises exposing the layer and developing itwith a primary aromatic amino developing agent in the presence in saidemulsion layer prior to development, of the coupler 2-(2,4-di-tert.amylphenoxybutyramido)-5 capronylaminophenol.

6. The method of producing a cyan photographic image in silver halideemulsion layer, which comprises exposing the layer and developing itwith a primary aromatic amino developing agent in the presence in saidemulsion. layer prior to development, of the coupler 2-(2,4-di-tert.amylphenoxybutyramido)-5-p-tert. amylbenzoylaminophenol.

7. The method of producing a cyan photographic image in silver halideemulsion layer, which comprises exposing the layer and developing itwith a primary aromatic amino developing agent in the presence in saidemulsion layer prior to development, of the coupler 1 l 2-capronylamino5 a (2,4-di-tert. amylphenoxybutyramido)-phenol.

8. A color-forming photographic emulsion comprising a gelatino-silver.halide emulsion layer containing dispersed particles of awater-insoluble, water-permeable coupler solvent selected from the classconsistingof cellulose esters, natural and synthetic resins, and organiccrystalloidal materials having a boiling point above about 175 C.,having dissolved therein a 2,5-diacylaminophenol coupler compound inwhich the acyl is derived from carboxylic acid.

9. A color-forming photographic emulsion comprising a gelatino-silverhalide emulsion layer containing dispersed particles of awater-insoluble, water-permeable coupler solvent selected from the classconsisting of cellulose esters, natural and synthetic resins, andorganic crystalloidal materials having a boiling point above about 175C., having dissolved therein a coupler compound having the formula:

in which X is selected from the class consisting of fatty acid acylradicals, aromatic carboxylic acyl radicals and aryloxy-substitutedfatty acid acyl radicals, and Y is selected from the class consisting offatty acid acyl radicals, aromatic carboxylic acyl radicals,aryloxy-substituted fatty acid acyl radicals, phenylcarbamyl fatty acidacyl radicals and furoyl radicals.

10. A color-forming photographic emulsion comprising a gelatino-silverhalide emulsion layer containing dispersed particles of awater-insoluble, water-permeable 12 coupler solvent having dissolvedtherein a coupler compound having the formula:

NHOOR ROCHN in which R represents an alkyl radical of from 4 to 15carbon atoms and R represents an aryloxyalkyl radical in which the alkylradical contains from 1 to 3 carbon atoms.

11. The emulsion of claim 8 in which the coupler compound is2(2-,4-di-tert. amylphenoxybutyramido)'-5- capronylamino-phenol.

12. The emulsion of claim 8 in which the coupler compound is2-(2,4-di-tert. amylphenoxybutyramido)-5- p-tert.amylbenzoyl-amino-phenol.

13. The emulsion of claim 8 inwhich the coupler compound is2-capronylamino-5-a-(2,4-di-tert. amylphenoxybutyramido-phenol.

14. The emulsion of claim 8 in which the coupler compound is2,5-bis-[a-(x-chloro-2,4-di-tert. amylphenoxy) -acetamido]-4,6-dichlorophenol.

15. The emulsion of claim 8 in which the coupler solvent is 2,4-di-tert.amyl phenol.

References Cited in the file of this patent UNITED STATES PATENTS

1. THE METHOD OF PRODUCING A CYAN PHOTOGRAPHIC IMAGE IN SILVER HALIDEEMULSION LAYER, WHICH COMPRISES EXPOSING THE LAYER AND DEVELOPING ITWITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT IN THE PRESENCE OF A2,5-DIACYLAMINOPHENOL COUPLER COMPOUND, IN WHICH THE ACYL IS DERIVEDFROM CARBOXYLIC ACID.